Three-dimensional memory device containing amorphous and crystalline blocking dielectric layers

ABSTRACT

A semiconductor structure includes an alternating stack of insulating layers and electrically conductive layers located over a substrate, memory openings vertically extending through the alternating stack, memory opening fill structures located in the memory openings, where each of the memory opening fill structures contains a memory film and a vertical semiconductor channel that extend vertically, and each memory film includes a crystalline blocking dielectric metal oxide layer, and a metal oxide amorphous dielectric nucleation layer located between each of the vertically neighboring electrically conductive layers and insulating layers, and located between each of the crystalline blocking dielectric metal oxide layers and each of the electrically conductive layers.

FIELD

The present disclosure relates generally to the field of semiconductordevices and specifically to a three-dimensional memory structurecontaining amorphous and crystalline blocking dielectric layers andmethods of making thereof.

BACKGROUND

Three-dimensional vertical NAND strings having one bit per cell aredisclosed in an article by T. Endoh, et al., titled “Novel Ultra HighDensity Memory With A Stacked-Surrounding Gate Transistor (S-SGT)Structured Cell”, IEDM Proc. (2001) 33-36.

SUMMARY

According to an aspect of the present disclosure, a method of forming asemiconductor structure is provided, which comprises: forming analternating stack of insulating layers and sacrificial material layersover a substrate; forming memory openings vertically extending throughthe alternating stack; forming memory opening fill structures in thememory openings, wherein each of the memory opening fill structurescomprises a memory film and a vertical semiconductor channel that extendvertically, and each memory film comprises a blocking dielectric metaloxide layer; forming backside recesses by removing the sacrificialmaterial layers selective to the insulating layers and the memoryopening fill structures; forming an amorphous dielectric nucleationlayer including an amorphous dielectric metal oxide material onphysically exposed surfaces of the insulating layers and outer sidewallsof the blocking dielectric metal oxide layers; and forming electricallyconductive layers in remaining volumes of the backside recessesemploying a nucleation process that forms a crystalline metallic lineron the amorphous dielectric nucleation layer.

According to another aspect of the present disclosure, a semiconductorstructure includes an alternating stack of insulating layers andelectrically conductive layers located over a substrate, memory openingsvertically extending through the alternating stack, memory opening fillstructures located in the memory openings, where each of the memoryopening fill structures contains a memory film and a verticalsemiconductor channel that extend vertically, and each memory filmincludes a crystalline blocking dielectric metal oxide layer, and ametal oxide amorphous dielectric nucleation layer located between eachof the vertically neighboring electrically conductive layers andinsulating layers, and located between each of the crystalline blockingdielectric metal oxide layers and each of the electrically conductivelayers.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic vertical cross-sectional view of an exemplarystructure after formation of at least one peripheral device and asemiconductor material layer according to an embodiment of the presentdisclosure.

FIG. 2 is a schematic vertical cross-sectional view of the exemplarystructure after formation of an alternating stack of insulating layersand sacrificial material layers according to an embodiment of thepresent disclosure.

FIG. 3 is a schematic vertical cross-sectional view of the exemplarystructure after formation of stepped surfaces and a retro-steppeddielectric material portion according to an embodiment of the presentdisclosure.

FIG. 4A is a schematic vertical cross-sectional view of the exemplarystructure after formation of memory openings and support openingsaccording to an embodiment of the present disclosure.

FIG. 4B is a top-down view of the exemplary structure of FIG. 4A. Thevertical plane A-A′ is the plane of the cross-section for FIG. 4A.

FIGS. 5A-5H are sequential schematic vertical cross-sectional views of amemory opening within the exemplary structure during formation of amemory stack structure, an optional dielectric core, and a drain regiontherein according to an embodiment of the present disclosure.

FIG. 6 is a schematic vertical cross-sectional view of the exemplarystructure after formation of memory stack structures and support pillarstructures according to an embodiment of the present disclosure.

FIG. 7A is a schematic vertical cross-sectional view of the exemplarystructure after formation of backside trenches according to anembodiment of the present disclosure.

FIG. 7B is a partial see-through top-down view of the exemplarystructure of FIG. 7A. The vertical plane A-A′ is the plane of theschematic vertical cross-sectional view of FIG. 7A.

FIG. 7C is a schematic vertical cross-sectional view along the verticalplane C-C′ of the exemplary structure of FIG. 7B.

FIG. 8 is a schematic vertical cross-sectional view of a region of theexemplary structure after formation of a source region underneath eachbackside trench according to an embodiment of the present disclosure.

FIG. 9A is a schematic vertical cross-sectional view of the exemplarystructure after formation of backside recesses according to anembodiment of the present disclosure.

FIG. 9B is a schematic vertical cross-section view of a region of theexemplary structure at the processing steps of FIG. 9A.

FIG. 10A is a schematic vertical cross-section view of a region of theexemplary structure after an oxidation process that includes an annealprocess according to an embodiment of the present disclosure.

FIG. 10B is a schematic vertical cross-section view of a region of theexemplary structure after formation of an amorphous dielectricnucleation layer according to an embodiment of the present disclosure.

FIG. 10C is a schematic vertical cross-section view of a region of theexemplary structure after formation of a crystalline metallic liner anda conductive fill material layer according to an embodiment of thepresent disclosure.

FIG. 11A is a schematic vertical cross-sectional view of the exemplarystructure after removal of portions of the conductive fill materiallayer, the crystalline metallic liner, and the amorphous dielectricnucleation layer located in the backside trenches or overlying acontact-level dielectric layer according to an embodiment of the presentdisclosure.

FIG. 11B is a partial see-through top-down view of the exemplarystructure of FIG. 11A. The vertical plane A-A′ is the plane of theschematic vertical cross-sectional view of FIG. 11A.

FIG. 11C is a schematic vertical cross-sectional view along the verticalplane C-C′ of the exemplary structure of FIG. 11B.

FIG. 12 is a schematic vertical cross-sectional view of the exemplarystructure after formation of an insulating spacer and a backside contactstructure according to an embodiment of the present disclosure.

FIG. 13A is a schematic vertical cross-sectional view of the exemplarystructure after formation of additional contact via structures accordingto an embodiment of the present disclosure.

FIG. 13B is a top-down view of the exemplary structure of FIG. 13A. Thevertical plane A-A′ is the plane of the schematic verticalcross-sectional view of FIG. 13A.

DETAILED DESCRIPTION

As discussed above, the embodiments of the present disclosure aredirected to a three-dimensional memory device containing crystalline andamorphous blocking dielectric layers, the various aspects of which aredescribed below. The embodiments of the disclosure can be employed toform various structures including a multilevel memory structure,non-limiting examples of which include semiconductor devices such asthree-dimensional monolithic memory array devices comprising a pluralityof NAND memory strings.

The drawings are not drawn to scale. Multiple instances of an elementmay be duplicated where a single instance of the element is illustrated,unless absence of duplication of elements is expressly described orclearly indicated otherwise. Ordinals such as “first,” “second,” and“third” are employed merely to identify similar elements, and differentordinals may be employed across the specification and the claims of theinstant disclosure. The same reference numerals refer to the sameelement or similar element. Unless otherwise indicated, elements havingthe same reference numerals are presumed to have the same compositionand the same function. Unless otherwise indicated, a “contact” betweenelements refers to a direct contact between elements that provides anedge or a surface shared by the elements. As used herein, a firstelement located “on” a second element can be located on the exteriorside of a surface of the second element or on the interior side of thesecond element. As used herein, a first element is located “directly on”a second element if there exist a physical contact between a surface ofthe first element and a surface of the second element. As used herein, afirst element is “electrically connected to” a second element if thereexists a conductive path consisting of at least one conductive materialbetween the first element and the second element. As used herein, a“prototype” structure or an “in-process” structure refers to a transientstructure that is subsequently modified in the shape or composition ofat least one component therein.

As used herein, a “layer” refers to a material portion including aregion having a thickness. A layer may extend over the entirety of anunderlying or overlying structure, or may have an extent less than theextent of an underlying or overlying structure. Further, a layer may bea region of a homogeneous or inhomogeneous continuous structure that hasa thickness less than the thickness of the continuous structure. Forexample, a layer may be located between any pair of horizontal planesbetween, or at, a top surface and a bottom surface of the continuousstructure. A layer may extend horizontally, vertically, and/or along atapered surface. A substrate may be a layer, may include one or morelayers therein, or may have one or more layer thereupon, thereabove,and/or therebelow.

As used herein, a first surface and a second surface are “verticallycoincident” with each other if the second surface overlies or underliesthe first surface and there exists a vertical plane or a substantiallyvertical plane that includes the first surface and the second surface. Asubstantially vertical plane is a plane that extends straight along adirection that deviates from a vertical direction by an angle less than5 degrees. A vertical plane or a substantially vertical plane isstraight along a vertical direction or a substantially verticaldirection, and may, or may not, include a curvature along a directionthat is perpendicular to the vertical direction or the substantiallyvertical direction.

A monolithic three-dimensional memory array is a memory array in whichmultiple memory levels are formed above a single substrate, such as asemiconductor wafer, with no intervening substrates. The term“monolithic” means that layers of each level of the array are directlydeposited on the layers of each underlying level of the array. Incontrast, two dimensional arrays may be formed separately and thenpackaged together to form a non-monolithic memory device. For example,non-monolithic stacked memories have been constructed by forming memorylevels on separate substrates and vertically stacking the memory levels,as described in U.S. Pat. No. 5,915,167 titled “Three-dimensionalStructure Memory.” The substrates may be thinned or removed from thememory levels before bonding, but as the memory levels are initiallyformed over separate substrates, such memories are not true monolithicthree-dimensional memory arrays. The various three-dimensional memorydevices of the present disclosure include a monolithic three-dimensionalNAND string memory device, and can be fabricated employing the variousembodiments described herein.

Generally, a semiconductor package (or a “package”) refers to a unitsemiconductor device that can be attached to a circuit board through aset of pins or solder balls. A semiconductor package may include asemiconductor chip (or a “chip”) or a plurality of semiconductor chipsthat are bonded thereamongst, for example, by flip-chip bonding oranother chip-to-chip bonding. A package or a chip may include a singlesemiconductor die (or a “die”) or a plurality of semiconductor dies. Adie is the smallest unit that can independently execute externalcommands or report status. Typically, a package or a chip with multipledies is capable of simultaneously executing as many number of externalcommands as the total number of planes therein. Each die includes one ormore planes. Identical concurrent operations can be executed in eachplane within a same die, although there may be some restrictions. Incase a die is a memory die, i.e., a die including memory elements,concurrent read operations, concurrent write operations, or concurrenterase operations can be performed in each plane within a same memorydie. In a memory die, each plane contains a number of memory blocks (or“blocks”), which are the smallest unit that can be erased by in a singleerase operation. Each memory block contains a number of pages, which arethe smallest units that can be selected for programming. A page is alsothe smallest unit that can be selected to a read operation.

Referring to FIG. 1, an exemplary structure according to an embodimentof the present disclosure is illustrated, which can be employed, forexample, to fabricate a device structure containing vertical NAND memorydevices. The exemplary structure includes a substrate (9, 10), which canbe a semiconductor substrate. The substrate can include a substratesemiconductor layer 9 and an optional semiconductor material layer 10.The substrate semiconductor layer 9 maybe a semiconductor wafer or asemiconductor material layer, and can include at least one elementalsemiconductor material (e.g., single crystal silicon wafer or layer), atleast one III-V compound semiconductor material, at least one II-VIcompound semiconductor material, at least one organic semiconductormaterial, or other semiconductor materials known in the art. Thesubstrate can have a major surface 7, which can be, for example, atopmost surface of the substrate semiconductor layer 9. The majorsurface 7 can be a semiconductor surface. In one embodiment, the majorsurface 7 can be a single crystalline semiconductor surface, such as asingle crystalline semiconductor surface.

As used herein, a “semiconducting material” refers to a material havingelectrical conductivity in the range from 1.0×10⁻⁵ S/m to 1.0×10⁵ S/m.As used herein, a “semiconductor material” refers to a material havingelectrical conductivity in the range from 1.0×10⁻⁵ S/m to 1.0 S/m in theabsence of electrical dopants therein, and is capable of producing adoped material having electrical conductivity in a range from 1.0 S/m to1.0×10⁵ S/m upon suitable doping with an electrical dopant. As usedherein, an “electrical dopant” refers to a p-type dopant that adds ahole to a valence band within a band structure, or an n-type dopant thatadds an electron to a conduction band within a band structure. As usedherein, a “conductive material” refers to a material having electricalconductivity greater than 1.0×10⁵ S/m. As used herein, an “insulatormaterial” or a “dielectric material” refers to a material havingelectrical conductivity less than 1.0×10⁻⁵ S/m. As used herein, a“heavily doped semiconductor material” refers to a semiconductormaterial that is doped with electrical dopant at a sufficiently highatomic concentration to become a conductive material either as formed asa crystalline material or if converted into a crystalline materialthrough an anneal process (for example, from an initial amorphousstate), i.e., to have electrical conductivity greater than 1.0×10⁵ S/m.A “doped semiconductor material” may be a heavily doped semiconductormaterial, or may be a semiconductor material that includes electricaldopants (i.e., p-type dopants and/or n-type dopants) at a concentrationthat provides electrical conductivity in the range from 1.0×10⁻⁵ S/m to1.0×10⁵ S/m. An “intrinsic semiconductor material” refers to asemiconductor material that is not doped with electrical dopants. Thus,a semiconductor material may be semiconducting or conductive, and may bean intrinsic semiconductor material or a doped semiconductor material. Adoped semiconductor material can be semiconducting or conductivedepending on the atomic concentration of electrical dopants therein. Asused herein, a “metallic material” refers to a conductive materialincluding at least one metallic element therein. All measurements forelectrical conductivities are made at the standard condition.

At least one semiconductor device 700 for a peripheral circuitry can beformed on a portion of the substrate semiconductor layer 9. The at leastone semiconductor device can include, for example, field effecttransistors. For example, at least one shallow trench isolationstructure 720 can be formed by etching portions of the substratesemiconductor layer 9 and depositing a dielectric material therein. Agate dielectric layer, at least one gate conductor layer, and a gate capdielectric layer can be formed over the substrate semiconductor layer 9,and can be subsequently patterned to form at least one gate structure(750, 752, 754, 758), each of which can include a gate dielectric 750, agate electrode (752, 754), and a gate cap dielectric 758. The gateelectrode (752, 754) may include a stack of a first gate electrodeportion 752 and a second gate electrode portion 754. At least one gatespacer 756 can be formed around the at least one gate structure (750,752, 754, 758) by depositing and anisotropically etching a dielectricliner. Active regions 730 can be formed in upper portions of thesubstrate semiconductor layer 9, for example, by introducing electricaldopants employing the at least one gate structure (750, 752, 754, 758)as masking structures. Additional masks may be employed as needed. Theactive region 730 can include source regions and drain regions of fieldeffect transistors. A first dielectric liner 761 and a second dielectricliner 762 can be optionally formed. Each of the first and seconddielectric liners (761, 762) can comprise a silicon oxide layer, asilicon nitride layer, and/or a dielectric metal oxide layer. As usedherein, silicon oxide includes silicon dioxide as well asnon-stoichiometric silicon oxides having more or less than two oxygenatoms for each silicon atoms. Silicon dioxide is preferred. In anillustrative example, the first dielectric liner 761 can be a siliconoxide layer, and the second dielectric liner 762 can be a siliconnitride layer. The least one semiconductor device for the peripheralcircuitry can contain a driver circuit for memory devices to besubsequently formed, which can include at least one NAND device.

A dielectric material such as silicon oxide can be deposited over the atleast one semiconductor device, and can be subsequently planarized toform a planarization dielectric layer 770. In one embodiment theplanarized top surface of the planarization dielectric layer 770 can becoplanar with a top surface of the dielectric liners (761, 762).Subsequently, the planarization dielectric layer 770 and the dielectricliners (761, 762) can be removed from an area to physically expose a topsurface of the substrate semiconductor layer 9. As used herein, asurface is “physically exposed” if the surface is in physical contactwith vacuum, or a gas phase material (such as air).

The optional semiconductor material layer 10, if present, can be formedon the top surface of the substrate semiconductor layer 9 prior to, orafter, formation of the at least one semiconductor device 700 bydeposition of a single crystalline semiconductor material, for example,by selective epitaxy. The deposited semiconductor material can be thesame as, or can be different from, the semiconductor material of thesubstrate semiconductor layer 9. The deposited semiconductor materialcan be any material that can be employed for the substrate semiconductorlayer 9 as described above. The single crystalline semiconductormaterial of the semiconductor material layer 10 can be in epitaxialalignment with the single crystalline structure of the substratesemiconductor layer 9. Portions of the deposited semiconductor materiallocated above the top surface of the planarization dielectric layer 770can be removed, for example, by chemical mechanical planarization (CMP).In this case, the semiconductor material layer 10 can have a top surfacethat is coplanar with the top surface of the planarization dielectriclayer 770.

The region (i.e., area) of the at least one semiconductor device 700 isherein referred to as a peripheral device region 200. The region inwhich a memory array is subsequently formed is herein referred to as amemory array region 100. A staircase region 300 for subsequently formingstepped surfaces of electrically conductive layers can be providedbetween the memory array region 100 and the peripheral device region200.

Referring to FIG. 2, a stack of an alternating plurality of firstmaterial layers (which can be insulating layers 32) and second materiallayers (which can be sacrificial material layer 42) is formed over thetop surface of the substrate (9, 10). As used herein, a “material layer”refers to a layer including a material throughout the entirety thereof.As used herein, an alternating plurality of first elements and secondelements refers to a structure in which instances of the first elementsand instances of the second elements alternate. Each instance of thefirst elements that is not an end element of the alternating pluralityis adjoined by two instances of the second elements on both sides, andeach instance of the second elements that is not an end element of thealternating plurality is adjoined by two instances of the first elementson both ends. The first elements may have the same thicknessthereamongst, or may have different thicknesses. The second elements mayhave the same thickness thereamongst, or may have different thicknesses.The alternating plurality of first material layers and second materiallayers may begin with an instance of the first material layers or withan instance of the second material layers, and may end with an instanceof the first material layers or with an instance of the second materiallayers. In one embodiment, an instance of the first elements and aninstance of the second elements may form a unit that is repeated withperiodicity within the alternating plurality.

Each first material layer includes a first material, and each secondmaterial layer includes a second material that is different from thefirst material. In one embodiment, each first material layer can be aninsulating layer 32, and each second material layer can be a sacrificialmaterial layer. In this case, the stack can include an alternatingplurality of insulating layers 32 and sacrificial material layers 42,and constitutes a prototype stack of alternating layers comprisinginsulating layers 32 and sacrificial material layers 42.

The stack of the alternating plurality is herein referred to as analternating stack (32, 42). In one embodiment, the alternating stack(32, 42) can include insulating layers 32 composed of the firstmaterial, and sacrificial material layers 42 composed of a secondmaterial different from that of insulating layers 32. The first materialof the insulating layers 32 can be at least one insulating material. Assuch, each insulating layer 32 can be an insulating material layer.Insulating materials that can be employed for the insulating layers 32include, but are not limited to, silicon oxide (including doped orundoped silicate glass), silicon nitride, silicon oxynitride,organosilicate glass (OSG), spin-on dielectric materials, dielectricmetal oxides that are commonly known as high dielectric constant(high-k) dielectric oxides (e.g., aluminum oxide, hafnium oxide, etc.)and silicates thereof, dielectric metal oxynitrides and silicatesthereof, and organic insulating materials. In one embodiment, the firstmaterial of the insulating layers 32 can be silicon oxide.

The second material of the sacrificial material layers 42 is asacrificial material that can be removed selective to the first materialof the insulating layers 32. As used herein, a removal of a firstmaterial is “selective to” a second material if the removal processremoves the first material at a rate that is at least twice the rate ofremoval of the second material. The ratio of the rate of removal of thefirst material to the rate of removal of the second material is hereinreferred to as a “selectivity” of the removal process for the firstmaterial with respect to the second material.

The sacrificial material layers 42 may comprise an insulating material,a semiconductor material, or a conductive material. The second materialof the sacrificial material layers 42 can be subsequently replaced withelectrically conductive electrodes which can function, for example, ascontrol gate electrodes of a vertical NAND device. Non-limiting examplesof the second material include silicon nitride, an amorphoussemiconductor material (such as amorphous silicon), and apolycrystalline semiconductor material (such as polysilicon). In oneembodiment, the sacrificial material layers 42 can be spacer materiallayers that comprise silicon nitride or a semiconductor materialincluding at least one of silicon and germanium.

In one embodiment, the insulating layers 32 can include silicon oxide,and sacrificial material layers can include silicon nitride sacrificialmaterial layers. The first material of the insulating layers 32 can bedeposited, for example, by chemical vapor deposition (CVD). For example,if silicon oxide is employed for the insulating layers 32, tetraethylorthosilicate (TEOS) can be employed as the precursor material for theCVD process. The second material of the sacrificial material layers 42can be formed, for example, CVD or atomic layer deposition (ALD).

The sacrificial material layers 42 can be suitably patterned so thatconductive material portions to be subsequently formed by replacement ofthe sacrificial material layers 42 can function as electricallyconductive electrodes, such as the control gate electrodes of themonolithic three-dimensional NAND string memory devices to besubsequently formed. The sacrificial material layers 42 may comprise aportion having a strip shape extending substantially parallel to themajor surface 7 of the substrate.

The thicknesses of the insulating layers 32 and the sacrificial materiallayers 42 can be in a range from 20 nm to 50 nm, although lesser andgreater thicknesses can be employed for each insulating layer 32 and foreach sacrificial material layer 42. The number of repetitions of thepairs of an insulating layer 32 and a sacrificial material layer (e.g.,a control gate electrode or a sacrificial material layer) 42 can be in arange from 2 to 1,024, and typically from 8 to 256, although a greaternumber of repetitions can also be employed. The top and bottom gateelectrodes in the stack may function as the select gate electrodes. Inone embodiment, each sacrificial material layer 42 in the alternatingstack (32, 42) can have a uniform thickness that is substantiallyinvariant within each respective sacrificial material layer 42.

While the present disclosure is described employing an embodiment inwhich the spacer material layers are sacrificial material layers 42 thatare subsequently replaced with electrically conductive layers,embodiments are expressly contemplated herein in which the sacrificialmaterial layers are formed as electrically conductive layers. In thiscase, steps for replacing the spacer material layers with electricallyconductive layers can be omitted.

Optionally, an insulating cap layer 70 can be formed over thealternating stack (32, 42). The insulating cap layer 70 includes adielectric material that is different from the material of thesacrificial material layers 42. In one embodiment, the insulating caplayer 70 can include a dielectric material that can be employed for theinsulating layers 32 as described above. The insulating cap layer 70 canhave a greater thickness than each of the insulating layers 32. Theinsulating cap layer 70 can be deposited, for example, by chemical vapordeposition. In one embodiment, the insulating cap layer 70 can be asilicon oxide layer.

Referring to FIG. 3, stepped surfaces are formed at a peripheral regionof the alternating stack (32, 42), which is herein referred to as aterrace region. As used herein, “stepped surfaces” refer to a set ofsurfaces that include at least two horizontal surfaces and at least twovertical surfaces such that each horizontal surface is adjoined to afirst vertical surface that extends upward from a first edge of thehorizontal surface, and is adjoined to a second vertical surface thatextends downward from a second edge of the horizontal surface. A steppedcavity is formed within the volume from which portions of thealternating stack (32, 42) are removed through formation of the steppedsurfaces. A “stepped cavity” refers to a cavity having stepped surfaces.

The terrace region is formed in the staircase region 300, which islocated between the memory array region 100 and the peripheral deviceregion 200 containing the at least one semiconductor device for theperipheral circuitry. The stepped cavity can have various steppedsurfaces such that the horizontal cross-sectional shape of the steppedcavity changes in steps as a function of the vertical distance from thetop surface of the substrate (9, 10). In one embodiment, the steppedcavity can be formed by repetitively performing a set of processingsteps. The set of processing steps can include, for example, an etchprocess of a first type that vertically increases the depth of a cavityby one or more levels, and an etch process of a second type thatlaterally expands the area to be vertically etched in a subsequent etchprocess of the first type. As used herein, a “level” of a structureincluding alternating plurality is defined as the relative position of apair of a first material layer and a second material layer within thestructure.

Each sacrificial material layer 42 other than a topmost sacrificialmaterial layer 42 within the alternating stack (32, 42) laterallyextends farther than any overlying sacrificial material layer 42 withinthe alternating stack (32, 42) in the terrace region. The terrace regionincludes stepped surfaces of the alternating stack (32, 42) thatcontinuously extend from a bottommost layer within the alternating stack(32, 42) to a topmost layer within the alternating stack (32, 42).

Each vertical step of the stepped surfaces can have the height of one ormore pairs of an insulating layer 32 and a sacrificial material layer.In one embodiment, each vertical step can have the height of a singlepair of an insulating layer 32 and a sacrificial material layer 42. Inanother embodiment, multiple “columns” of staircases can be formed alonga first horizontal direction hd1 such that each vertical step has theheight of a plurality of pairs of an insulating layer 32 and asacrificial material layer 42, and the number of columns can be at leastthe number of the plurality of pairs. Each column of staircase can bevertically offset among one another such that each of the sacrificialmaterial layers 42 has a physically exposed top surface in a respectivecolumn of staircases. In the illustrative example, two columns ofstaircases are formed for each block of memory stack structures to besubsequently formed such that one column of staircases providephysically exposed top surfaces for odd-numbered sacrificial materiallayers 42 (as counted from the bottom) and another column of staircasesprovide physically exposed top surfaces for even-numbered sacrificialmaterial layers (as counted from the bottom). Configurations employingthree, four, or more columns of staircases with a respective set ofvertical offsets among the physically exposed surfaces of thesacrificial material layers 42 may also be employed. Each sacrificialmaterial layer 42 has a greater lateral extent, at least along onedirection, than any overlying sacrificial material layers 42 such thateach physically exposed surface of any sacrificial material layer 42does not have an overhang. In one embodiment, the vertical steps withineach column of staircases may be arranged along the first horizontaldirection hd1, and the columns of staircases may be arranged along asecond horizontal direction hd2 that is perpendicular to the firsthorizontal direction hd1. In one embodiment, the first horizontaldirection hd1 may be perpendicular to the boundary between the memoryarray region 100 and the staircase region 300.

A retro-stepped dielectric material portion 65 (i.e., an insulating fillmaterial portion) can be formed in the stepped cavity by deposition of adielectric material therein. For example, a dielectric material such assilicon oxide can be deposited in the stepped cavity. Excess portions ofthe deposited dielectric material can be removed from above the topsurface of the insulating cap layer 70, for example, by chemicalmechanical planarization (CMP). The remaining portion of the depositeddielectric material filling the stepped cavity constitutes theretro-stepped dielectric material portion 65. As used herein, a“retro-stepped” element refers to an element that has stepped surfacesand a horizontal cross-sectional area that increases monotonically as afunction of a vertical distance from a top surface of a substrate onwhich the element is present. If silicon oxide is employed for theretro-stepped dielectric material portion 65, the silicon oxide of theretro-stepped dielectric material portion 65 may, or may not, be dopedwith dopants such as B, P, and/or F.

Optionally, drain select level isolation structures 72 can be formedthrough the insulating cap layer 70 and a subset of the sacrificialmaterial layers 42 located at drain select levels. The drain selectlevel isolation structures 72 can be formed, for example, by formingdrain select level isolation trenches and filling the drain select levelisolation trenches with a dielectric material such as silicon oxide.Excess portions of the dielectric material can be removed from above thetop surface of the insulating cap layer 70.

Referring to FIGS. 4A and 4B, a lithographic material stack (not shown)including at least a photoresist layer can be formed over the insulatingcap layer 70 and the retro-stepped dielectric material portion 65, andcan be lithographically patterned to form openings therein. The openingsinclude a first set of openings formed over the memory array region 100and a second set of openings formed over the staircase region 300. Thepattern in the lithographic material stack can be transferred throughthe insulating cap layer 70 or the retro-stepped dielectric materialportion 65, and through the alternating stack (32, 42) by at least oneanisotropic etch that employs the patterned lithographic material stackas an etch mask. Portions of the alternating stack (32, 42) underlyingthe openings in the patterned lithographic material stack are etched toform memory openings 49 and support openings 19. As used herein, a“memory opening” refers to a structure in which memory elements, such asa memory stack structure, is subsequently formed. As used herein, a“support opening” refers to a structure in which a support structure(such as a support pillar structure) that mechanically supports otherelements is subsequently formed. The memory openings 49 are formedthrough the insulating cap layer 70 and the entirety of the alternatingstack (32, 42) in the memory array region 100. The support openings 19are formed through the retro-stepped dielectric material portion 65 andthe portion of the alternating stack (32, 42) that underlie the steppedsurfaces in the staircase region 300.

The memory openings 49 extend through the entirety of the alternatingstack (32, 42). The support openings 19 extend through a subset oflayers within the alternating stack (32, 42). The chemistry of theanisotropic etch process employed to etch through the materials of thealternating stack (32, 42) can alternate to optimize etching of thefirst and second materials in the alternating stack (32, 42). Theanisotropic etch can be, for example, a series of reactive ion etches.The sidewalls of the memory openings 49 and the support openings 19 canbe substantially vertical, or can be tapered. The patterned lithographicmaterial stack can be subsequently removed, for example, by ashing.

The memory openings 49 and the support openings 19 can extend from thetop surface of the alternating stack (32, 42) to at least the horizontalplane including the topmost surface of the semiconductor material layer10. In one embodiment, an overetch into the semiconductor material layer10 may be optionally performed after the top surface of thesemiconductor material layer 10 is physically exposed at a bottom ofeach memory opening 49 and each support opening 19. The overetch may beperformed prior to, or after, removal of the lithographic materialstack. In other words, the recessed surfaces of the semiconductormaterial layer 10 may be vertically offset from the un-recessed topsurfaces of the semiconductor material layer 10 by a recess depth. Therecess depth can be, for example, in a range from 1 nm to 50 nm,although lesser and greater recess depths can also be employed. Theoveretch is optional, and may be omitted. If the overetch is notperformed, the bottom surfaces of the memory openings 49 and the supportopenings 19 can be coplanar with the topmost surface of thesemiconductor material layer 10.

Each of the memory openings 49 and the support openings 19 may include asidewall (or a plurality of sidewalls) that extends substantiallyperpendicular to the topmost surface of the substrate. A two-dimensionalarray of memory openings 49 can be formed in the memory array region100. A two-dimensional array of support openings 19 can be formed in thestaircase region 300. The substrate semiconductor layer 9 and thesemiconductor material layer 10 collectively constitutes a substrate (9,10), which can be a semiconductor substrate. Alternatively, thesemiconductor material layer 10 may be omitted, and the memory openings49 and the support openings 19 can be extend to a top surface of thesubstrate semiconductor layer 9.

FIGS. 5A-5H illustrate structural changes in a memory opening 49, whichis one of the memory openings 49 in the exemplary structure of FIGS. 4Aand 4B. The same structural change occurs simultaneously in each of theother memory openings 49 and in each of the support openings 19.

Referring to FIG. 5A, a memory opening 49 in the exemplary devicestructure of FIGS. 4A and 4B is illustrated. The memory opening 49extends through the insulating cap layer 70, the alternating stack (32,42), and optionally into an upper portion of the semiconductor materiallayer 10. At this processing step, each support opening 19 can extendthrough the retro-stepped dielectric material portion 65, a subset oflayers in the alternating stack (32, 42), and optionally through theupper portion of the semiconductor material layer 10. The recess depthof the bottom surface of each memory opening with respect to the topsurface of the semiconductor material layer 10 can be in a range from 0nm to 30 nm, although greater recess depths can also be employed.Optionally, the sacrificial material layers 42 can be laterally recessedpartially to form lateral recesses (not shown), for example, by anisotropic etch.

Referring to FIG. 5B, an optional pedestal channel portion (e.g., anepitaxial pedestal) 11 can be formed at the bottom portion of eachmemory opening 49 and each support openings 19, for example, byselective epitaxy. Each pedestal channel portion 11 comprises a singlecrystalline semiconductor material in epitaxial alignment with thesingle crystalline semiconductor material of the semiconductor materiallayer 10. In one embodiment, the top surface of each pedestal channelportion 11 can be formed above a horizontal plane including the topsurface of a bottommost sacrificial material layer 42. In this case, asource select gate electrode can be subsequently formed by replacing thebottommost sacrificial material layer 42 with a conductive materiallayer. The pedestal channel portion 11 can be a portion of a transistorchannel that extends between a source region to be subsequently formedin the substrate (9, 10) and a drain region to be subsequently formed inan upper portion of the memory opening 49. A memory cavity 49′ ispresent in the unfilled portion of the memory opening 49 above thepedestal channel portion 11. In one embodiment, the pedestal channelportion 11 can comprise single crystalline silicon. In one embodiment,the pedestal channel portion 11 can have a doping of the firstconductivity type, which is the same as the conductivity type of thesemiconductor material layer 10 that the pedestal channel portioncontacts. If a semiconductor material layer 10 is not present, thepedestal channel portion 11 can be formed directly on the substratesemiconductor layer 9, which can have a doping of the first conductivitytype.

Referring to FIG. 5C, a stack of layers including an optional siliconoxide liner 501, an amorphous blocking dielectric metal oxide layer 51′,a blocking dielectric semiconductor compound layer 52, a charge storagelayer 54, a tunneling dielectric layer 56, and an optional firstsemiconductor channel layer 601 can be sequentially deposited in thememory openings 49.

The optional silicon oxide liner 501 is an optional layer that may, ormay not, be present. If present, the silicon oxide liner 501 can includea conformal layer of silicon oxide, and can have a thickness in a rangefrom 0.5 nm to 5 nm, such as from 1 nm to 3 nm. The silicon oxide liner501 may be subsequently employed as an etch stop layer during formationof backside recesses.

The amorphous blocking dielectric metal oxide layer 51′ can be formed asan amorphous dielectric metal oxide layer by a conformal depositionprocess. The amorphous dielectric metal oxide layer includes anamorphous dielectric material that includes at least one metallicelement and at least oxygen. The amorphous dielectric metal oxide layermay consist essentially of the at least one metallic element and oxygen,or may consist essentially of the at least one metallic element, oxygen,and at least one non-metallic element such as nitrogen. In oneembodiment, the amorphous blocking dielectric metal oxide layer 51′ caninclude an amorphous dielectric metal oxide having a dielectric constantgreater than 7.9, i.e., having a dielectric constant greater than thedielectric constant of silicon nitride.

Non-limiting examples of dielectric metal oxide materials that may beemployed for the amorphous blocking dielectric metal oxide layer 51′include aluminum oxide (Al₂O₃), hafnium oxide (HfO₂), lanthanum oxide(LaO₂), yttrium oxide (Y₂O₃), tantalum oxide (Ta₂O₅), silicates thereof,nitrogen-doped compounds thereof, alloys thereof, and stacks thereof.The amorphous blocking dielectric metal oxide layer 51′ can bedeposited, for example, by chemical vapor deposition (CVD), atomic layerdeposition (ALD), pulsed laser deposition (PLD), liquid source mistedchemical deposition, or a combination thereof. The thickness of theamorphous blocking dielectric metal oxide layer 51′ can be in a rangefrom 1 nm to 20 nm, although lesser and greater thicknesses can also beemployed. The amorphous blocking dielectric metal oxide layer 51′ cansubsequently function as a blocking dielectric material portion thatblocks leakage of stored electrical charges to control gate electrodes.

In one embodiment, the amorphous blocking dielectric metal oxide layer51′ consists essentially of a dielectric metal oxide material. Theamorphous blocking dielectric metal oxide layer 51′ can be formed as anamorphous dielectric metal oxide layer, and is subsequently convertedinto a crystalline (e.g., polycrystalline) blocking dielectric metaloxide layer by an anneal process, as shown in FIG. 5D. In oneembodiment, the amorphous blocking dielectric metal oxide layer 51′consists essentially of an aluminum oxide material, which is hereinreferred to as first aluminum oxide material. The first aluminum oxidematerial can be deposited in an amorphous phase, and is subsequentlyconverted into a polycrystalline aluminum oxide material layer 51. Theamorphous blocking dielectric metal oxide layer 51′ is formed directlyon the silicon oxide liner 501 (if present) or on sidewalls of theinsulating layers 32 and the sacrificial material layers 42 as acontinuous material layer within each of the memory openings 49.

The blocking dielectric semiconductor compound layer 52 can include adielectric semiconductor compound material such as silicon oxide,silicon oxynitride, or a combination thereof. In one embodiment, theblocking dielectric semiconductor compound layer 52 can include, and/orcan consist essentially of, silicon oxide. In this case, the dielectricsemiconductor compound material can be formed by a conformal depositionmethod such as low pressure chemical vapor deposition, atomic layerdeposition, or a combination thereof. The thickness of the blockingdielectric semiconductor compound layer 52 can be in a range from 1 nmto 20 nm, such as 2 nm to 5 nm, although lesser and greater thicknessescan also be employed.

Subsequently, the charge storage layer 54 can be formed. In oneembodiment, the charge storage layer 54 can be a continuous layer orpatterned discrete portions of a charge trapping material including adielectric charge trapping material, which can be, for example, siliconnitride. Alternatively, the charge storage layer 54 can include acontinuous layer or patterned discrete portions of a conductive materialsuch as doped polysilicon or a metallic material that is patterned intomultiple electrically isolated portions (e.g., floating gates), forexample, by being formed within lateral recesses into sacrificialmaterial layers 42. In one embodiment, the charge storage layer 54includes a silicon nitride layer. In one embodiment, the sacrificialmaterial layers 42 and the insulating layers 32 can have verticallycoincident sidewalls, and the charge storage layer 54 can be formed as asingle continuous layer.

In another embodiment, the sacrificial material layers 42 can belaterally recessed with respect to the sidewalls of the insulatinglayers 32, and a combination of a deposition process and an anisotropicetch process can be employed to form the charge storage layer 54 as aplurality of memory material portions that are vertically spaced apart.While the present disclosure is described employing an embodiment inwhich the charge storage layer 54 is a single continuous layer,embodiments are expressly contemplated herein in which the chargestorage layer 54 is replaced with a plurality of memory materialportions (which can be charge trapping material portions or electricallyisolated conductive material portions) that are vertically spaced apart.

The charge storage layer 54 can be formed as a single charge storagelayer of homogeneous composition, or can include a stack of multiplecharge storage layers. The multiple charge storage layers, if employed,can comprise a plurality of spaced-apart floating gate material layersthat contain conductive materials (e.g., metal such as tungsten,molybdenum, tantalum, titanium, platinum, ruthenium, and alloys thereof,or a metal silicide such as tungsten silicide, molybdenum silicide,tantalum silicide, titanium silicide, nickel silicide, cobalt silicide,or a combination thereof) and/or semiconductor materials (e.g.,polycrystalline or amorphous semiconductor material including at leastone elemental semiconductor element or at least one compoundsemiconductor material). Alternatively or additionally, the chargestorage layer 54 may comprise an insulating charge trapping material,such as one or more silicon nitride segments. Alternatively, the chargestorage layer 54 may comprise conductive nanoparticles such as metalnanoparticles, which can be, for example, ruthenium nanoparticles. Thecharge storage layer 54 can be formed, for example, by chemical vapordeposition (CVD), atomic layer deposition (ALD), physical vapordeposition (PVD), or any suitable deposition technique for storingelectrical charges therein. The thickness of the charge storage layer 54can be in a range from 2 nm to 20 nm, although lesser and greaterthicknesses can also be employed.

The tunneling dielectric layer 56 includes a dielectric material throughwhich charge tunneling can be performed under suitable electrical biasconditions. The charge tunneling may be performed through hot-carrierinjection or by Fowler-Nordheim tunneling induced charge transferdepending on the mode of operation of the monolithic three-dimensionalNAND string memory device to be formed. The tunneling dielectric layer56 can include silicon oxide, silicon nitride, silicon oxynitride,dielectric metal oxides (such as aluminum oxide and hafnium oxide),dielectric metal oxynitride, dielectric metal silicates, alloys thereof,and/or combinations thereof. In one embodiment, the tunneling dielectriclayer 56 can include a stack of a first silicon oxide layer, a siliconoxynitride layer, and a second silicon oxide layer, which is commonlyknown as an ONO stack. In one embodiment, the tunneling dielectric layer56 can include a silicon oxide layer that is substantially free ofcarbon or a silicon oxynitride layer that is substantially free ofcarbon. The thickness of the tunneling dielectric layer 56 can be in arange from 2 nm to 20 nm, although lesser and greater thicknesses canalso be employed.

The optional first semiconductor channel layer 601 includes asemiconductor material such as at least one elemental semiconductormaterial, at least one III-V compound semiconductor material, at leastone II-VI compound semiconductor material, at least one organicsemiconductor material, or other semiconductor materials known in theart. In one embodiment, the first semiconductor channel layer 601includes amorphous silicon or polysilicon. The first semiconductorchannel layer 601 can be formed by a conformal deposition method such aslow pressure chemical vapor deposition (LPCVD). The thickness of thefirst semiconductor channel layer 601 can be in a range from 2 nm to 10nm, although lesser and greater thicknesses can also be employed. Amemory cavity 49′ is formed in the volume of each memory opening 49 thatis not filled with the deposited material layers (52, 54, 56, 601).

Referring to FIG. 5D, the optional first semiconductor channel layer601, the tunneling dielectric layer 56, the charge storage layer 54, theblocking dielectric semiconductor compound layer 52, the amorphousblocking dielectric metal oxide layer 51′ and the optional silicon oxideliner 501 are sequentially anisotropically etched employing at least oneanisotropic etch process. The portions of the first semiconductorchannel layer 601, the tunneling dielectric layer 56, the charge storagelayer 54, the blocking dielectric semiconductor compound layer 52, theamorphous blocking dielectric metal oxide layer 51′ and the siliconoxide liner 501 located above the top surface of the insulating caplayer 70 can be removed by the at least one anisotropic etch process.Further, the horizontal portions of the first semiconductor channellayer 601, the tunneling dielectric layer 56, the charge storage layer54, the blocking dielectric semiconductor compound layer 52, theamorphous blocking dielectric metal oxide layer 51′ and the siliconoxide liner 501 at a bottom of each memory cavity 49′ can be removed toform openings in remaining portions thereof. Each of the firstsemiconductor channel layer 601, the tunneling dielectric layer 56, thecharge storage layer 54, the blocking dielectric semiconductor compoundlayer 52, the amorphous blocking dielectric metal oxide layer 51′, andthe silicon oxide liner 501 can be etched by a respective anisotropicetch process employing a respective etch chemistry, which may, or maynot, be the same for the various material layers.

Each remaining portion of the first semiconductor channel layer 601 canhave a tubular configuration. The charge storage layer 54 can comprise acharge trapping material or a floating gate material. In one embodiment,each charge storage layer 54 can include a vertical stack of chargestorage regions that store electrical charges upon programming. In oneembodiment, the charge storage layer 54 can be a charge storage layer inwhich each portion adjacent to the sacrificial material layers 42constitutes a charge storage region.

A surface of the pedestal channel portion 11 (or a surface of thesemiconductor material layer 10 in case the pedestal channel portions 11are not employed) can be physically exposed underneath the openingthrough the first semiconductor channel layer 601, the tunnelingdielectric layer 56, the charge storage layer 54, the blockingdielectric semiconductor compound layer 52, the amorphous blockingdielectric metal oxide layer 51′ and the silicon oxide liner 501.Optionally, the physically exposed semiconductor surface at the bottomof each memory cavity 49′ can be vertically recessed so that therecessed semiconductor surface underneath the memory cavity 49′ isvertically offset from the topmost surface of the pedestal channelportion 11 (or of the semiconductor material layer 10 in case pedestalchannel portions 11 are not employed) by a recess distance. A tunnelingdielectric layer 56 is located over the charge storage layer 54. Eachcontiguous set of the optional silicon oxide liner 501, an amorphousblocking dielectric metal oxide layer 51′, a blocking dielectricsemiconductor compound layer 52, a charge storage layer 54, and atunneling dielectric layer 56 in a memory opening 49 constitutes amemory film 50, which includes a plurality of charge storage regions(comprising the charge storage layer 54) that are insulated fromsurrounding materials by the blocking dielectric semiconductor compoundlayer 52 and the tunneling dielectric layer 56. In one embodiment, thefirst semiconductor channel layer 601, the tunneling dielectric layer56, the charge storage layer 54, the blocking dielectric semiconductorcompound layer 52, and the amorphous blocking dielectric metal oxidelayer 51′ in each memory film 50 can have vertically coincidentsidewalls.

An anneal process may be carried out at this step in the process inwhich each amorphous blocking dielectric metal oxide layer 51′ isconverted into a respective crystalline blocking dielectric metal oxidelayer 51. The amorphous dielectric material in the amorphous blockingdielectric metal oxide layers 51′ crystalizes during the anneal process,and is converted into a crystalline blocking dielectric metal oxidematerial. Thus, the crystalline blocking dielectric metal oxide layers51 include, and/or consist essentially of, a crystalline dielectricmetal oxide material. If the amorphous blocking dielectric metal oxidelayers 51′ include, and/or consist essentially of, a first amorphousaluminum oxide material, the crystalline blocking dielectric metal oxidelayers 51 include, and/or consist essentially of, a polycrystallinealuminum oxide material. Alternatively, the anneal may be conducted at alater step.

Referring to FIG. 5E, a second semiconductor channel layer 602 can bedeposited directly on the semiconductor surface of the pedestal channelportion 11 or the semiconductor material layer 10 if the pedestalchannel portion 11 is omitted, and directly on the first semiconductorchannel layer 601. The second semiconductor channel layer 602 includes asemiconductor material such as at least one elemental semiconductormaterial, at least one III-V compound semiconductor material, at leastone II-VI compound semiconductor material, at least one organicsemiconductor material, or other semiconductor materials known in theart. In one embodiment, the second semiconductor channel layer 602includes amorphous silicon or polysilicon. The second semiconductorchannel layer 602 can be formed by a conformal deposition method such aslow pressure chemical vapor deposition (LPCVD). The thickness of thesecond semiconductor channel layer 602 can be in a range from 2 nm to 10nm, although lesser and greater thicknesses can also be employed. Thesecond semiconductor channel layer 602 may partially fill the memorycavity 49′ in each memory opening, or may fully fill the cavity in eachmemory opening.

The materials of the first semiconductor channel layer 601 and thesecond semiconductor channel layer 602 are collectively referred to as asemiconductor channel material. In other words, the semiconductorchannel material is a set of all semiconductor material in the firstsemiconductor channel layer 601 and the second semiconductor channellayer 602.

Referring to FIG. 5F, in case the memory cavity 49′ in each memoryopening is not completely filled by the second semiconductor channellayer 602, a dielectric core layer 62L can be deposited in the memorycavity 49′ to fill any remaining portion of the memory cavity 49′ withineach memory opening. The dielectric core layer 62L includes a dielectricmaterial such as silicon oxide or organosilicate glass. The dielectriccore layer 62L can be deposited by a conformal deposition method such aslow pressure chemical vapor deposition (LPCVD), or by a self-planarizingdeposition process such as spin coating.

Referring to FIG. 5G, the horizontal portion of the dielectric corelayer 62L can be removed, for example, by a recess etch from above thetop surface of the second semiconductor channel layer 602. Further, thematerial of the dielectric core layer 62L can be vertically recessedselective to the semiconductor material of the second semiconductorchannel layer 602 into each memory opening 49 down to a depth between afirst horizontal plane including the top surface of the insulating caplayer 70 and a second horizontal plane including the bottom surface ofthe insulating cap layer 70. Each remaining portion of the dielectriccore layer 62L constitutes a dielectric core 62.

Referring to FIG. 5H, a doped semiconductor material having a doping ofa second conductivity type can be deposited within each recessed regionabove the dielectric cores 62. The second conductivity type is theopposite of the first conductivity type. For example, if the firstconductivity type is p-type, the second conductivity type is n-type, andvice versa. The dopant concentration of the doped semiconductor materialcan be in a range from 5.0×10¹⁹/cm³ to 2.0×10²¹/cm³, although lesser andgreater dopant concentrations can also be employed. The dopedsemiconductor material can be, for example, doped polysilicon.

Excess portions of the deposited semiconductor material can be removedfrom above the top surface of the insulating cap layer 70, for example,by chemical mechanical planarization (CMP) or a recess etch. Eachremaining portion of the semiconductor material having a doping of thesecond conductively type constitutes a drain region 63. The horizontalportion of the second semiconductor channel layer 602 located above thetop surface of the insulating cap layer 70 can be concurrently removedby a planarization process. Each remaining portion of the secondsemiconductor channel layer 602 can be located entirety within a memoryopening 49 or entirely within a support opening 19.

Each remaining portion of the doped semiconductor material having adoping of the second conductivity type constitutes a drain region 63.Each adjoining pair of a first semiconductor channel layer 601 and asecond semiconductor channel layer 602 can collectively form a verticalsemiconductor channel 60 through which electrical current can flow whena vertical NAND device including the vertical semiconductor channel 60is turned on. A tunneling dielectric layer 56 is surrounded by a chargestorage layer 54, and laterally surrounds a portion of the verticalsemiconductor channel 60. Each adjoining set of a tunneling dielectriclayer 56, a charge storage layer 54, a blocking dielectric semiconductorcompound layer 52, a crystalline blocking dielectric metal oxide layer51 and an optional silicon oxide liner 501 collectively constitute amemory film 50, which includes a vertical stack of memory elements thatcan store a respective data bit with a macroscopic retention time. Asused herein, a macroscopic retention time refers to a retention timesuitable for operation of a memory device as a permanent memory devicesuch as a retention time in excess of 24 hours.

Each combination of a memory film 50 and a vertical semiconductorchannel 60 within a memory opening 49 constitutes a memory stackstructure 55. The memory stack structure 55 is a combination of asemiconductor channel 60, a tunneling dielectric layer 56, a pluralityof memory elements comprising portions of the charge storage layer 54, ablocking dielectric semiconductor compound layer 52, the crystallineblocking dielectric metal oxide layer 51 and the optional silicon oxideliner 501. Each combination of a pedestal channel portion 11 (ifpresent), a memory stack structure 55, a dielectric core 62, and a drainregion 63 within a memory opening 49 is herein referred to as a memoryopening fill structure 58. Each combination of a pedestal channelportion 11 (if present), a memory film 50, a vertical semiconductorchannel 60, a dielectric core 62, and a drain region 63 within eachsupport opening 19 fills the respective support openings 19, andconstitutes a support pillar structure.

Generally, memory opening fill structures 58 are formed in the memoryopenings 49. Each of the memory opening fill structures 58 comprises amemory film 50 and a vertical semiconductor channel 60 that extendvertically. Each memory film 50 comprises a crystalline blockingdielectric metal oxide layer 51. Each of the crystalline blockingdielectric metal oxide layers 51 is formed within a respective one ofthe memory openings 49. A blocking dielectric semiconductor compoundlayer (e.g., a silicon oxide layer) 52 can be formed on a respective oneof the crystalline blocking dielectric metal oxide layers 51 within eachof the memory openings 49. A charge storage layer 54 and a tunnelingdielectric layer 56 are formed on a respective one of the blockingdielectric semiconductor compound layers 52 within each of the memoryopenings 49. Drain regions 63 are formed in the memory opening fillstructures 58 at an upper end of a respective one of the semiconductorchannels 60.

Referring to FIG. 6, the exemplary structure is illustrated afterformation of memory opening fill structures 58 and support pillarstructure 20 within the memory openings 49 and the support openings 19,respectively. An instance of a memory opening fill structure 58 can beformed within each memory opening 49 of the structure of FIGS. 4A and4B. An instance of the support pillar structure 20 can be formed withineach support opening 19 of the structure of FIGS. 4A and 4B.

Each memory stack structure 55 includes a vertical semiconductor channel60, which may comprise multiple semiconductor channel layers (601, 602),and a memory film 50. The memory film 50 may comprise a tunnelingdielectric layer 56 laterally surrounding the vertical semiconductorchannel 60, a vertical stack of charge storage regions (comprising acharge storage layer 54) laterally surrounding the tunneling dielectriclayer 56, a blocking dielectric semiconductor compound layer 52, and acrystalline blocking dielectric metal oxide layer 51. While the presentdisclosure is described employing the illustrated configuration for thememory stack structure, the methods of the present disclosure can beapplied to alternative memory stack structures including different layerstacks or structures for the memory film 50 and/or for the verticalsemiconductor channel 60.

Referring to FIGS. 7A-7C, a contact level dielectric layer 73 can beformed over the alternating stack (32, 42) of insulating layer 32 andsacrificial material layers 42, and over the memory stack structures 55and the support pillar structures 20. The contact level dielectric layer73 includes a dielectric material that is different from the dielectricmaterial of the sacrificial material layers 42. For example, the contactlevel dielectric layer 73 can include silicon oxide. The contact leveldielectric layer 73 can have a thickness in a range from 50 nm to 500nm, although lesser and greater thicknesses can also be employed.

A photoresist layer (not shown) can be applied over the contact leveldielectric layer 73, and is lithographically patterned to form openingsin areas between clusters of memory stack structures 55. The pattern inthe photoresist layer can be transferred through the contact leveldielectric layer 73, the alternating stack (32, 42) and/or theretro-stepped dielectric material portion 65 employing an anisotropicetch to form backside trenches 79, which vertically extend from the topsurface of the contact level dielectric layer 73 at least to the topsurface of the substrate (9, 10), and laterally extend through thememory array region 100 and the staircase region 300.

In one embodiment, the backside trenches 79 can laterally extend along afirst horizontal direction hd1 and can be laterally spaced apart amongone another along a second horizontal direction hd2 that isperpendicular to the first horizontal direction hd1. The memory stackstructures 55 can be arranged in rows that extend along the firsthorizontal direction hd1. The drain select level isolation structures 72can laterally extend along the first horizontal direction hd1. Eachbackside trench 79 can have a uniform width that is invariant along thelengthwise direction (i.e., along the first horizontal direction hd1).Each drain select level isolation structure 72 can have a uniformvertical cross-sectional profile along vertical planes that areperpendicular to the first horizontal direction hd1 that is invariantwith translation along the first horizontal direction hd1. Multiple rowsof memory stack structures 55 can be located between a neighboring pairof a backside trench 79 and a drain select level isolation structure 72,or between a neighboring pair of drain select level isolation structures72. In one embodiment, the backside trenches 79 can include a sourcecontact opening in which a source contact via structure can besubsequently formed. The photoresist layer can be removed, for example,by ashing.

Referring to FIG. 8, dopants of the second conductivity can be implantedinto surface portions of the semiconductor material layer 10 thatunderlies the backside trenches 79. A source region 61 can be formed ata surface portion of the semiconductor material layer 10 under eachbackside trench 79. The dose of the dopants of the second conductivitytype is selected such that a p-n junction is formed between each sourceregion 61 and unimplanted portions of the semiconductor material layer10. The atomic concentration of the dopants of the second conductivitytype in the source regions 61 can be in a range from 5.0×10¹⁹/cm³ to2.0×10²⁰/cm³, although lesser and greater dopant concentrations can alsobe employed. Due to the straggle of the implanted dopant atoms duringthe implantation process and lateral diffusion of the implanted dopantatoms during a subsequent activation anneal process, each source region61 can have a lateral extent greater than the lateral extent of arespective overlying backside trench 79. The source regions 61 can beamorphized due to the heavy dose of the implanted dopants of the secondconductivity type, and thus, the dopants of the second conductivity typein the source regions 61 are not electrically active until a subsequentanneal process that recrystallizes the source regions 61.

An upper portion of the semiconductor material layer 10 that extendsbetween the source region 61 and the plurality of pedestal channelportions 11 constitutes a horizontal semiconductor channel 59 for aplurality of field effect transistors. The horizontal semiconductorchannel 59 is connected to multiple vertical semiconductor channels 60through respective pedestal channel portions 11. The horizontalsemiconductor channel 59 contacts the source region 61 and the pluralityof pedestal channel portions 11. Semiconductor channels (59, 11, 60)extend between each source region 61 and a respective set of drainregions 63. The semiconductor channels (59, 11, 60) include the verticalsemiconductor channels 60 of the memory stack structures 55.

Referring to FIG. 9B, an etchant that selectively etches the secondmaterial of the sacrificial material layers 42 with respect to the firstmaterial of the insulating layers 32 can be introduced into the backsidetrenches 79, for example, employing an etch process. If present, thesilicon oxide liners 501 may be employed as etch stop layers. Backsiderecesses 43 are formed in volumes from which the sacrificial materiallayers 42 are removed. The removal of the second material of thesacrificial material layers 42 can be selective to the first material ofthe insulating layers 32, the material of the retro-stepped dielectricmaterial portion 65, the semiconductor material of the semiconductormaterial layer 10, and the material of the outermost layer of the memoryfilms 50. In one embodiment, the sacrificial material layers 42 caninclude silicon nitride, and the materials of the insulating layers 32and the retro-stepped dielectric material portion 65 can be selectedfrom silicon oxide and dielectric metal oxides.

The etch process that removes the second material selective to the firstmaterial and the outermost layer of the memory films 50 can be a wetetch process employing a wet etch solution, or can be a gas phase (dry)etch process in which the etchant is introduced in a vapor phase intothe backside trenches 79. For example, if the sacrificial materiallayers 42 include silicon nitride, the etch process can be a wet etchprocess in which the exemplary structure is immersed within a wet etchtank including phosphoric acid, which etches silicon nitride selectiveto silicon oxide, silicon, and various other materials employed in theart. The support pillar structure 20, the retro-stepped dielectricmaterial portion 65, and the memory stack structures 55 providestructural support while the backside recesses 43 are present withinvolumes previously occupied by the sacrificial material layers 42.

In case a silicon oxide liner 501 is present in each memory film 50,physically exposed portions of the silicon oxide liners 501 can beetched selective to the material of the crystalline blocking dielectricmetal oxide layer 51 by a terminal etch step, which can include a wetetch process employing dilute hydrofluoric acid. Each backside recess 43can be a laterally extending cavity having a lateral dimension that isgreater than the vertical extent of the cavity. In other words, thelateral dimension of each backside recess 43 can be greater than theheight of the backside recess 43. A plurality of backside recesses 43can be formed in the volumes from which the second material of thesacrificial material layers 42 is removed. The memory openings in whichthe memory stack structures 55 are formed are herein referred to asfront side openings or front side cavities in contrast with the backsiderecesses 43. In one embodiment, the memory array region 100 comprises anarray of monolithic three-dimensional NAND strings having a plurality ofdevice levels disposed above the substrate (9, 10). In this case, eachbackside recess 43 can define a space for receiving a respective wordline of the array of monolithic three-dimensional NAND strings.

Each of the plurality of backside recesses 43 can extend substantiallyparallel to the top surface of the substrate (9, 10). A backside recess43 can be vertically bounded by a top surface of an underlyinginsulating layer 32 and a bottom surface of an overlying insulatinglayer 32. In one embodiment, each backside recess 43 can have a uniformheight throughout.

Referring to FIG. 10A, physically exposed surface portions of theoptional pedestal channel portions 11 and the source regions 61 can beconverted into dielectric oxide portions by a thermal oxidation process.The thermal oxidation process can convert a surface portion of eachpedestal channel portion 11 into a tubular dielectric spacer 116, andcan convert each physically exposed surface portion of the sourceregions 61 into a planar dielectric portion 616. In one embodiment, eachtubular dielectric spacer 116 can be topologically homeomorphic to atorus, i.e., generally ring-shaped. As used herein, an element istopologically homeomorphic to a torus if the shape of the element can becontinuously stretched without destroying a hole or forming a new holeinto the shape of a torus.

The tubular dielectric spacers 116 include a dielectric oxide materialthat contains the same semiconductor element as the pedestal channelportions 11 and additionally includes oxygen atoms. Thus, the materialof the tubular dielectric spacers 116 comprises, and/or consistsessentially of, a dielectric oxide of the semiconductor material of thepedestal channel portions 11. Likewise, each planar dielectric portion616 includes a dielectric oxide material that contains the samesemiconductor element as the semiconductor material layer 10 andadditionally includes oxygen atoms. In one embodiment, the planardielectric portions 616 can include a dielectric oxide of thesemiconductor material of the semiconductor material layer 10.

The thermal oxidation of the surface portions of the semiconductormaterial layer 10 and the pedestal channel portions 11 into dielectricmaterial portions (such as the tubular dielectric spacers 116 and theplanar dielectric portions 616) can be performed at an elevatedtemperature. The thermal oxidation process can be performed at anelevated temperature in an oxidizing ambient. The thermal oxidation canbe performed by a rapid thermal anneal (RTA) process with a peaktemperature in a range from 950 degrees Celsius to 1,050 degreesCelsius. The duration of the peak temperature during the RTA process canbe in a range from 1 second to 30 seconds, although lesser and greaterdurations can also be employed. Alternatively, the thermal oxidation canbe performed by a furnace anneal process with a lower peak temperatureand a longer duration of the peak temperature than the RTA process.

The temperature and the duration of the anneal process can be selectedsuch that the dopants of the second conductivity type in the sourceregions 61 and the drain region 63 are electrically activated. If thedopants of the first conductivity type in the semiconductor channels 60are not already activated, the dopants of the first conductivity type inthe semiconductor channels 60 can be activated during the annealprocess. The amorphous doped semiconductor material portions in thesource regions 61 can be recrystallized into single crystalline dopedsemiconductor material portions during the anneal process. The dopantsof the second conductivity type are incorporated into substitutionalsites in the single crystalline structure of the source regions 61during the anneal process, and the source regions 61 can be convertedinto a conductive material, i.e., a material having electricalconductivity greater than 1.0×10⁵ S/m. Likewise, if the drain regions 63and the semiconductor channels 60 include any amorphous semiconductormaterial, such an amorphous semiconductor material can be crystalizedinto a polycrystalline semiconductor material, such as dopedpolysilicon.

Referring to FIG. 10B, an amorphous dielectric nucleation layer 84including an amorphous dielectric metal oxide material can be can beformed on physically exposed surfaces of the backside trenches 79 andthe backside recesses 43. The amorphous dielectric nucleation layer 84can be conformally formed directly on physically exposed surfaces of theinsulating layers 32 and outer sidewalls of the crystalline blockingdielectric metal oxide layers 51. The amorphous dielectric metal oxidematerial of the amorphous dielectric nucleation layer 84 includes anamorphous dielectric metal oxide material such as aluminum oxide(Al₂O₃), hafnium oxide (HfO₂), lanthanum oxide (LaO₂), yttrium oxide(Y₂O₃), or tantalum oxide (Ta₂O₅) in an amorphous phase. The amorphousdielectric nucleation layer 84 may comprise the same or differentcomposition of material as the crystalline blocking dielectric metaloxide layer 51.

The thickness of the amorphous dielectric nucleation layer 84 can beminimized while providing a coverage of more than 90%, such as more than98%, of the physically exposed surfaces of the insulating layers 32 andthe crystalline blocking dielectric metal oxide layers 51 in the memoryfilms 50. For example, the thickness of the amorphous dielectricnucleation layer 84 can be in a range from 0.3 nm to 1 nm, such as from0.3 nm to 0.6 nm. The amorphous dielectric nucleation layer 84 may bethinner (e.g., at least two times thinner, such as two to ten timesthinner) than the crystalline blocking dielectric metal oxide layer 51.Minimizing the thickness of the amorphous dielectric nucleation layer 84provides the advantage of increasing the remaining volume of thebackside recesses 43 in which electrically conductive layers can besubsequently formed. The amorphous dielectric metal oxide material ofthe amorphous dielectric nucleating layer 84 provides a nucleationsurface for a crystalline metallic liner to be subsequently deposited.Without wishing to be bound by a particular theory, it is believed thatthe crystalline metallic liner to be subsequently deposited can nucleatewith a larger grain size on an amorphous material of the amorphousdielectric nucleating layer 84 than on a crystalline nucleation surface,and which results in improved fluorine blocking property.

In one embodiment, the amorphous dielectric nucleation layer 84 can beformed by a conformal deposition process such as atomic layer deposition(ALD). The amorphous dielectric nucleation layer 84 can consistessentially of an amorphous aluminum oxide material. In case thecrystalline blocking dielectric metal oxide layers 51 includes a firstamorphous aluminum oxide material in a crystalline phase, the amorphousaluminum oxide material of the amorphous dielectric nucleation layer 84is herein referred to as a second aluminum oxide material. The firstaluminum oxide material can be deposited in an amorphous phase duringformation of the memory opening fill structures 58, and can besubsequently converted into a polycrystalline aluminum oxide materialprior to formation of the amorphous dielectric nucleation layer 84. Inone embodiment, each of the crystalline blocking dielectric metal oxidelayers 51 consists essentially of a first aluminum oxide material in apolycrystalline phase, and the amorphous dielectric nucleation layer 84consists essentially of a second aluminum oxide material in an amorphousphase.

Referring to FIG. 10C, electrically conductive layers 46 can bedeposited in remaining volumes of the backside recesses 43 employing anucleation process that forms a crystalline metallic liner 46A on theamorphous dielectric nucleation layer 84. The crystalline metallic liner46A can be deposited directly on the physically exposed surfaces of theamorphous dielectric nucleation layer 84. The crystalline metallic liner46A includes an electrically conductive metallic material that canfunction as a diffusion barrier layer and/or adhesion promotion layerfor a metallic fill material to be subsequently deposited. Thecrystalline metallic liner 46A can include a conductive metallic nitridematerial such as TiN, TaN, or WN. In one embodiment, the crystallinemetallic liner 46A can be deposited by a conformal deposition processsuch as chemical vapor deposition (CVD) or atomic layer deposition(ALD). The thickness of the crystalline metallic liner 46A can be in arange from 1.5 nm to 6 nm, such as from 2 nm to 4 nm, although lesserand greater thicknesses can also be employed. In one embodiment, thecrystalline metallic liner 46A can consist essentially of a conductivemetal nitride such as TiN. The amorphous dielectric nucleation layer 84is deposited in an amorphous phase and remains amorphous until afterformation of the electrically conductive layers 46.

According to an aspect of the present disclosure, the crystallinemetallic liner 46A can be formed directly on the amorphous dielectricnucleation layer 84. The crystalline metallic liner 46A is laterallyspaced from the crystalline blocking dielectric metal oxide layers 51 byvertically-extending cylindrical portions of the amorphous dielectricnucleation layer 84. Further, the crystalline metallic liner 46A isvertically spaced from the insulating layers 32 byhorizontally-extending portions of the amorphous dielectric nucleationlayer 84. In other words, the crystalline sidewall surfaces of thecrystalline blocking dielectric metal oxide layers 51 are covered by thevertical cylindrical portions of the amorphous dielectric nucleationlayer 84, and horizontal silicon oxide surfaces of the insulating layers32 can be covered by horizontally-extending portions of the amorphousdielectric nucleation layer 84. Without wishing to be bound by aparticular theory, it is believed that nucleation characteristics of thecrystalline metallic liner 46A are determined by the surface propertiesof the amorphous dielectric nucleation layer 84. The amorphous nature ofthe physically exposed surfaces of the amorphous dielectric nucleationlayer 84 is believed to provide nucleation of the metallic nitridematerial of the crystalline metallic liner 46A with a larger grain thana crystalline nucleation surface or a surface of silicon oxide.

Without wishing to be bound by a particular theory, the amorphoussurface of the amorphous metal oxide dielectric material in theamorphous dielectric nucleation layer 84 (such as the amorphous surfaceof an amorphous aluminum oxide material) may improve the morphology ofthe crystalline metallic liner 46A by making the coverage of thecrystalline metallic liner 46A more uniform and improving the continuityof the crystalline metallic liner 46A, and thereby reducing thethickness variations in the crystalline metallic liner 46A. Further, theamorphous surface of the amorphous metal oxide dielectric material inthe amorphous dielectric nucleation layer 84 may increase the averagegrain size of the crystalline metallic liner 46A.

The uniform thickness of the crystalline metallic liner 46A and thereduction of grain boundaries (due to larger grain sizes) in thecrystalline metallic liner 46A can enhance the effectiveness of thecrystalline metallic liner 46A as a fluorine-diffusion-barrierstructure, and thus, reduces fluorine diffusion from a metallic fillmaterial (e.g., tungsten) to be subsequently deposited in remainingvolumes of the backside recesses 43 toward the insulating layers 32and/or toward the crystalline blocking dielectric metal oxide layers 51.As discussed above, the thickness of the amorphous dielectric nucleationlayer 84 can be minimized to a monolayer level, such as a range from 0.3nm to 1 nm, to minimize the total volume of the backside recesses 43that is occupied by the amorphous dielectric nucleation layer 84. Thus,the crystalline blocking dielectric metal oxide layers 51 can functionas an effective blocking dielectric for the charge storage layers 54,and leakage or tunneling of electrical charges through the crystallineblocking dielectric metal oxide layers 51 can be reduced or prevented.The amorphous dielectric nucleation layer 84 is employed as a thinnucleation template layer that is thinner than the crystalline blockingdielectric metal oxide layers 51 at least by a factor of two, such as atleast a factor of three, and induces formation of a crystalline metallicliner 46A with more uniform thickness, less grain boundaries, and largeraverage grain sizes that improves a fluorine barrier property of thematerial of the crystalline metallic liner 46A and induces formation oflarge grains in a metal fill material to be subsequently deposited.

A metal fill material is deposited in the plurality of backside recesses43, on the sidewalls of the at least one the backside trench 79, andover the top surface of the contact level dielectric layer 73 to form ametallic fill material layer 46B. The metallic fill material can bedeposited by a conformal deposition method, which can be, for example,chemical vapor deposition (CVD), atomic layer deposition (ALD),electroless plating, electroplating, or a combination thereof. In oneembodiment, the metallic fill material layer 46B can consist essentiallyof at least one elemental metal. The at least one elemental metal of themetallic fill material layer 46B can be selected, for example, fromtungsten, cobalt, ruthenium, titanium, and tantalum. In one embodiment,the metallic fill material layer 46B can consist essentially of a singleelemental metal, such as tungsten. In one embodiment, the metallic fillmaterial layer 46B can be deposited employing a fluorine-containingprecursor gas such as WF₆. In one embodiment, the metallic fill materiallayer 46B can be a tungsten layer including a residual level of fluorineatoms as impurities. The metallic fill material layer 46B is spaced fromthe insulating layers 32 and the memory stack structures 55 by thecrystalline metallic liner 46A, which is a crystalline metallic linerthat blocks diffusion of fluorine atoms therethrough.

A plurality of electrically conductive layers 46 can be formed in theplurality of backside recesses 43, and a continuous electricallyconductive material layer 46L can be formed on the sidewalls of eachbackside trench 79 and over the contact level dielectric layer 73. Eachelectrically conductive layer 46 includes a portion of the crystallinemetallic liner 46A and a portion of the metallic fill material layer 46Bthat are located between a vertically neighboring pair of dielectricmaterial layers such as a pair of insulating layers 32. The continuouselectrically conductive material layer 46L includes a continuous portionof the crystalline metallic liner 46A and a continuous portion of themetallic fill material layer 46B that are located in the backsidetrenches 79 or above the contact level dielectric layer 73.

Each sacrificial material layer 42 can be replaced with an electricallyconductive layer 46. A backside cavity 79′ is present in the portion ofeach backside trench 79 that is not filled with the amorphous dielectricnucleation layer 84 and the continuous electrically conductive materiallayer 46L. A tubular dielectric spacer 116 laterally surrounds apedestal channel portion 11. A bottommost electrically conductive layer46 laterally surrounds each tubular dielectric spacer 116 upon formationof the electrically conductive layers 46.

Referring to FIGS. 11A-11C, the deposited metallic material of thecontinuous electrically conductive material layer 46L is etched backfrom the sidewalls of each backside trench 79 and from above the contactlevel dielectric layer 73, for example, by an isotropic wet etch, ananisotropic dry etch, or a combination thereof. Each remaining portionof the deposited metallic material in the backside recesses 43constitutes an electrically conductive layer 46. Each electricallyconductive layer 46 can be a conductive line structure. Thus, thesacrificial material layers 42 are replaced with the electricallyconductive layers 46.

Each electrically conductive layer 46 can function as a combination of aplurality of control gate electrodes located at a same level and a wordline electrically interconnecting, i.e., electrically shorting, theplurality of control gate electrodes located at the same level. Theplurality of control gate electrodes within each electrically conductivelayer 46 are the control gate electrodes for the vertical memory devicesincluding the memory stack structures 55. In other words, eachelectrically conductive layer 46 can be a word line that functions as acommon control gate electrode for the plurality of vertical memorydevices.

In one embodiment, the removal of the continuous electrically conductivematerial layer 46L can be selective to the material of the amorphousdielectric nucleation layer 84. In this case, a horizontal portion ofthe amorphous dielectric nucleation layer 84 can be present at thebottom of each backside trench 79. In another embodiment, the removal ofthe continuous electrically conductive material layer 46L may not beselective to the material of the amorphous dielectric nucleation layer84. In this embodiment, the amorphous dielectric nucleation layer 84exposed in the backside trench after removal of the continuouselectrically conductive material layer 46L and the planar dielectricportions 616 can be removed during removal of the continuouselectrically conductive material layer 46L. A backside cavity is presentwithin each backside trench 79.

Referring to FIG. 12, an insulating material layer can be formed in thebackside trenches 79 and over the contact level dielectric layer 73 by aconformal deposition process. Exemplary conformal deposition processesinclude, but are not limited to, chemical vapor deposition and atomiclayer deposition. The insulating material layer includes an insulatingmaterial such as silicon oxide, silicon nitride, a dielectric metaloxide, an organosilicate glass, or a combination thereof. In oneembodiment, the insulating material layer can include silicon oxide. Theinsulating material layer can be formed, for example, by low pressurechemical vapor deposition (LPCVD) or atomic layer deposition (ALD). Thethickness of the insulating material layer can be in a range from 1.5 nmto 60 nm, although lesser and greater thicknesses can also be employed.

If the amorphous dielectric nucleation layer 84 is still present at aperiphery of each backside trench 79, then the insulating material layercan be formed directly on surfaces of the amorphous dielectricnucleation layer 84 and directly on the sidewalls of the electricallyconductive layers 46. If the amorphous dielectric nucleation layer 84 isnot present at a periphery of each backside trench 79, then theinsulating material layer can be formed directly on sidewalls of theinsulating layers 32 and directly on sidewalls of the electricallyconductive layers 46.

An anisotropic etch is performed to remove horizontal portions of theinsulating material layer from above the contact level dielectric layer73 and at the bottom of each backside trench 79. Each remaining portionof the insulating material layer constitutes an insulating spacer 74.Any remaining portions of the amorphous dielectric nucleation layer 84and the planar dielectric portion exposed at the bottom of theinsulating spacer 74 in in the backside trench 79 are also removed. Abackside cavity is present within a volume surrounded by each insulatingspacer 74. A top surface of a respective source region 61 can bephysically exposed at the bottom of each backside trench 79.

A backside contact via structure 76 can be formed within each backsidecavity. Each contact via structure 76 can fill a respective backsidecavity. The contact via structures 76 can be formed by depositing atleast one conductive material in the remaining unfilled volume (i.e.,the backside cavity) of the backside trench 79. For example, the atleast one conductive material can include a conductive liner 76A and aconductive fill material portion 76B. The conductive liner 76A caninclude a conductive metallic liner such as TiN, TaN, WN, TiC, TaC, WC,an alloy thereof, or a stack thereof. The thickness of the conductiveliner 76A can be in a range from 3 nm to 30 nm, although lesser andgreater thicknesses can also be employed. The conductive fill materialportion 76B can include a metal or a metallic alloy. For example, theconductive fill material portion 76B can include W, Cu, Al, Co, Ru, Ni,an alloy thereof, or a stack thereof.

The at least one conductive material can be planarized employing thecontact level dielectric layer 73 overlying the alternating stack (32,46) as a stopping layer. If chemical mechanical planarization (CMP)process is employed, the contact level dielectric layer 73 can beemployed as a CMP stopping layer. Each remaining continuous portion ofthe at least one conductive material in the backside trenches 79constitutes a backside contact via structure 76. The backside contactvia structure 76 extends through the alternating stack (32, 46), andcontacts a top surface of a respective source region 61.

Referring to FIGS. 13A and 13B, additional contact via structures (88,86, 8P) can be formed through the contact level dielectric layer 73, andoptionally through the retro-stepped dielectric material portion 65. Forexample, drain contact via structures 88 can be formed through thecontact level dielectric layer 73 on each drain region 63. Word linecontact via structures 86 can be formed on the electrically conductivelayers 46 through the contact level dielectric layer 73, and through theretro-stepped dielectric material portion 65. Peripheral device contactvia structures 8P can be formed through the retro-stepped dielectricmaterial portion 65 directly on respective nodes of the peripheraldevices.

The exemplary structures can include a three-dimensional memory device.In one embodiment, the three-dimensional memory device comprises amonolithic three-dimensional NAND memory device. The electricallyconductive layers 46 can comprise, or can be electrically connected to,a respective word line of the monolithic three-dimensional NAND memorydevice. The substrate (9, 10) can comprise a silicon substrate. Thevertical NAND memory device can comprise an array of monolithicthree-dimensional NAND strings over the silicon substrate. At least onememory cell (comprising a portion of a charge storage layer 54 at alevel of an electrically conductive layer 46) in a first device level ofthe array of monolithic three-dimensional NAND strings can be locatedover another memory cell (comprising another portion of the chargestorage layer 54 at a level of another electrically conductive layer 46)in a second device level of the array of monolithic three-dimensionalNAND strings. The silicon substrate can contain an integrated circuitcomprising a driver circuit (comprising a subset of the least onesemiconductor device 700) for the memory device located thereon. Theelectrically conductive layers 46 can comprise a plurality of controlgate electrodes having a strip shape extending substantially parallel tothe top surface of the substrate (9, 10), e.g., between a pair ofbackside trenches 79. The plurality of control gate electrodes comprisesat least a first control gate electrode located in a first device leveland a second control gate electrode located in a second device level.The array of monolithic three-dimensional NAND strings can comprise: aplurality of semiconductor channels (59, 11, 60), wherein at least oneend portion 60 of each of the plurality of semiconductor channels (59,11, 60) extends substantially perpendicular to a top surface of thesubstrate (9, 10) and comprising a respective one of the verticalsemiconductor channels 60; and a plurality of charge storage elements(comprising portions of the memory films 50, i.e., portions of thecharge storage layer 54). Each charge storage element can be locatedadjacent to a respective one of the plurality of semiconductor channels(59, 11, 60).

Referring to all drawings and according to various embodiments of thepresent disclosure, a semiconductor structure includes an alternatingstack of insulating layers 32 and electrically conductive layers 46located over a substrate (9, 10); memory openings 49 verticallyextending through the alternating stack (32, 46), and memory openingfill structures 58 located in the memory openings 49, wherein each ofthe memory opening fill structures 58 comprises a memory film 50 and avertical semiconductor channel 60 that extend vertically, and eachmemory film 50 comprises a blocking dielectric metal oxide layer 51, anda metal oxide amorphous dielectric nucleation layer 84 located betweeneach of the vertically neighboring electrically conductive layers 46 andinsulating layers 32, and located between each of the crystallineblocking dielectric metal oxide layers 51 and each of the electricallyconductive layers 46.

In one embodiment, each of the electrically conductive layers 46comprises a respective crystalline metallic nitride liner 46A thatcontacts the amorphous dielectric nucleation layer 84 and respectivetungsten conductive fill material portion 46B that is embedded in therespective crystalline metallic nitride liner. The amorphous dielectricnucleation layer 84 contacts a sidewall of the blocking dielectric metaloxide layer 51 in the memory stack structure.

In one embodiment, drain regions 63 are located in the memory openingfill structures 58, and can contact an upper end of a respective one ofthe semiconductor channels 60.

In one embodiment, each of the memory opening fill structures 58comprises a silicon oxide blocking dielectric layer 52 located on arespective one of the crystalline blocking dielectric metal oxide layers51. Each of the memory opening fill structures 58 also comprises acharge storage layer 54 and a tunneling dielectric layer 56 located thesilicon oxide blocking dielectric layer 52, and each of thesemiconductor channels 60 is located on a respective one of thetunneling dielectric layers 56 in each memory opening fill structure.

In one embodiment, each of the crystalline blocking dielectric metaloxide layers 51 consists essentially of a polycrystalline aluminum oxidematerial, and the amorphous dielectric nucleation layer 84 consistsessentially of an amorphous aluminum oxide material. Each of thecrystalline blocking dielectric metal oxide layers 51 is thicker thanthe amorphous dielectric nucleation layer 84.

The various embodiments of the present disclosure can be employed toprovide a more uniform nucleation for the crystalline metallic liners46A, to enhance thickness uniformity of the crystalline metallic liners46A, to increase the average grain size of the crystalline metallicliners 46A, and to enhance effectiveness of the crystalline metallicliners 46A as a fluorine diffusion barrier layer through reduction ofgrain boundaries. At the same time, the thickness of the amorphousdielectric nucleation layer 84 is minimized while providing a continuouscoverage of the crystalline blocking dielectric metal oxide layers 51and the insulating layers 32, and provide more volume for theelectrically conductive layers 46 so that the resistance of eachelectrically conductive layer 46 can be reduced through increase involume. Further, the large grain size of the crystalline metallic liners46A can induce formation of large grains in the metallic fill materiallayers 46B, thereby reducing the resistivity of metallic fill materiallayers 46B.

Although the foregoing refers to particular preferred embodiments, itwill be understood that the disclosure is not so limited. It will occurto those of ordinary skill in the art that various modifications may bemade to the disclosed embodiments and that such modifications areintended to be within the scope of the disclosure. Compatibility ispresumed among all embodiments that are not alternatives of one another.The word “comprise” or “include” contemplates all embodiments in whichthe word “consist essentially of” or the word “consists of” replaces theword “comprise” or “include,” unless explicitly stated otherwise. Wherean embodiment employing a particular structure and/or configuration isillustrated in the present disclosure, it is understood that the presentdisclosure may be practiced with any other compatible structures and/orconfigurations that are functionally equivalent provided that suchsubstitutions are not explicitly forbidden or otherwise known to beimpossible to one of ordinary skill in the art. All of the publications,patent applications and patents cited herein are incorporated herein byreference in their entirety.

What is claimed is:
 1. A method of forming a semiconductor structure,comprising: forming an alternating stack of insulating layers andsacrificial material layers over a substrate; forming memory openingsvertically extending through the alternating stack; forming memoryopening fill structures in the memory openings, wherein each of thememory opening fill structures comprises a memory film and a verticalsemiconductor channel that extend vertically, and each memory filmcomprises a blocking dielectric metal oxide layer; forming backsiderecesses by removing the sacrificial material layers selective to theinsulating layers and the memory opening fill structures; forming anamorphous dielectric nucleation layer including an amorphous dielectricmetal oxide material directly on physically exposed surfaces of theinsulating layers and directly on outer sidewalls of the blockingdielectric metal oxide layers; and forming electrically conductivelayers in remaining volumes of the backside recesses employing anucleation process that forms a crystalline metallic liner directly onthe amorphous dielectric nucleation layer.
 2. The method of claim 1,wherein the blocking dielectric metal oxide layers are formed asamorphous dielectric metal oxide layers, and are subsequently convertedinto crystalline blocking dielectric metal oxide layers by an annealprocess.
 3. The method of claim 2, wherein the amorphous dielectricmetal oxide material of the amorphous dielectric nucleation layer isdeposited directly on the crystalline blocking dielectric metal oxidelayers.
 4. The method of claim 2, further comprising: forming drainregions in the memory opening fill structures at an upper end of arespective one of the semiconductor channels; and forming source regionsin, or on, upper portions of the substrate.
 5. The method of claim 1,further comprising: forming a silicon oxide liner directly on a sidewallof each memory opening, wherein each of the blocking dielectric metaloxide layers is formed directly on the silicon oxide liner within arespective one of the memory openings; and removing portions of thesilicon oxide liner that are located at levels of the backside recesseswithout removing portions of the silicon oxide liner that are located atlevels of the insulating layers after formation of the backsiderecesses, wherein sidewall segments of the blocking dielectric metaloxide layers are physically exposed to the backside recesses; andwherein the amorphous dielectric nucleation layer is formed directly onsurfaces of remaining segments of the silicon oxide liner that remain atlevels of the insulating layers.
 6. The method of claim 1, furthercomprising forming a blocking dielectric semiconductor compound layer ona respective one of the blocking dielectric metal oxide layers withineach of the memory openings.
 7. The method of claim 6, furthercomprising forming a charge storage layer and a tunneling dielectriclayer on a respective one of the blocking dielectric semiconductorcompound layers within each of the memory openings, wherein each of thememory films comprises a respective blocking dielectric metal oxidelayer, a respective blocking dielectric semiconductor compound layer, arespective charge storage layer, and a respective tunneling dielectriclayer, and wherein each of the semiconductor channels is formed on arespective one of the tunneling dielectric layers.
 8. The method ofclaim 1, wherein: each of the blocking dielectric metal oxide layersconsists essentially of a first aluminum oxide material; and theamorphous dielectric nucleation layer consists essentially of a secondaluminum oxide material in an amorphous phase.
 9. The method of claim 8,wherein: the first aluminum oxide material is deposited in an amorphousphase and is subsequently converted into a polycrystalline aluminumoxide material prior to formation of the amorphous dielectric nucleationlayer; and the amorphous dielectric nucleation layer is deposited in anamorphous phase and remains amorphous until after formation of theelectrically conductive layers.
 10. The method of claim 9, wherein:wherein each of the blocking dielectric metal oxide layers is thickerthan the amorphous dielectric nucleation layer; the amorphous dielectricnucleation layer has a thickness in a range from 0.3 nm to 1 nm; and thecrystalline metallic liner comprises a conductive metallic nitridematerial.
 11. The method of claim 1, further comprising: formingbackside trenches through the alternating stack after formation of thememory opening fill structures; isotropically etching the sacrificialmaterial layers selective to the insulating layers and the memoryopening fill structures by introducing an isotropic etchant into thebackside trenches; conformally depositing the amorphous dielectricnucleation layer on physically exposed surfaces of the backside trenchesand the backside recesses; and filling remaining volumes of the backsiderecesses with a conductive fill material after formation of thecrystalline metallic liner on the amorphous dielectric nucleation layer.12. The method of claim 1, further comprising: forming stepped surfacesin a staircase region by patterning the alternating stack; forming aretro-stepped dielectric material portion of the stepped surfaces of thealternating stack; and forming contact via structures on a respectiveone of the electrically conducive layers through the retro-steppeddielectric material portion.
 13. A semiconductor structure comprising:an alternating stack of insulating layers and electrically conductivelayers located over a substrate; memory openings vertically extendingthrough the alternating stack; memory opening fill structures located inthe memory openings, wherein each of the memory opening fill structurescomprises a memory film and a vertical semiconductor channel that extendvertically, and each memory film comprises a crystalline blockingdielectric metal oxide layer; and a metal oxide amorphous dielectricnucleation layer located between each of the vertically neighboringelectrically conductive layers and insulating layers, and locatedbetween each of the crystalline blocking dielectric metal oxide layersand each of the electrically conductive layers, wherein each of theelectrically conductive layers is in direct contact with the metal oxideamorphous dielectric nucleation layer.
 14. The semiconductor structureof claim 13, wherein each of the electrically conductive layerscomprises a respective crystalline metallic nitride liner that contactsthe amorphous dielectric nucleation layer and respective tungstenconductive fill material portion that is embedded in the respectivecrystalline metallic nitride liner.
 15. The semiconductor structure ofclaim 13, wherein the amorphous dielectric nucleation layer contacts asidewall of the blocking dielectric metal oxide layer in the memoryopening fill structure.
 16. The semiconductor structure of claim 13,further comprising drain regions located in the memory opening fillstructures and contacting an upper end of a respective one of thesemiconductor channels.
 17. The semiconductor structure of claim 13,wherein each of the memory opening fill structures comprises: a siliconoxide blocking dielectric layer located on a respective one of thecrystalline blocking dielectric metal oxide layers; and vertical stacksof silicon oxide liners contacting an outer sidewall of the respectiveone of the crystalline blocking dielectric metal oxide layers andlocated at levels of the insulating layers and in direct contact withthe metal oxide amorphous dielectric nucleation layer.
 18. Thesemiconductor structure of claim 17, wherein: each of the memory openingfill structures comprises a charge storage layer and a tunnelingdielectric layer located the silicon oxide blocking dielectric layer;and each of the semiconductor channels is located on a respective one ofthe tunneling dielectric layers in each memory opening fill structure.19. The semiconductor structure of claim 13, wherein: each of thecrystalline blocking dielectric metal oxide layers consists essentiallyof a polycrystalline aluminum oxide material; and the amorphousdielectric nucleation layer consists essentially of an amorphousaluminum oxide material.
 20. The semiconductor structure of claim 19,wherein each of the crystalline blocking dielectric metal oxide layersis thicker than the amorphous dielectric nucleation layer.